CN111836718A - Laminate, container, and infusion bag - Google Patents

Laminate, container, and infusion bag Download PDF

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Publication number
CN111836718A
CN111836718A CN201980018505.1A CN201980018505A CN111836718A CN 111836718 A CN111836718 A CN 111836718A CN 201980018505 A CN201980018505 A CN 201980018505A CN 111836718 A CN111836718 A CN 111836718A
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China
Prior art keywords
hydrogenated
heat
layer
laminate
conjugated diene
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Granted
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CN201980018505.1A
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Chinese (zh)
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CN111836718B (en
Inventor
渡边直哉
石原稔久
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Amhibi Innovation Consulting Co ltd
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Amhibi Innovation Consulting Co ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
    • A61J1/10—Bag-type containers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/14—Details; Accessories therefor
    • A61J1/1468—Containers characterised by specific material properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
    • A61J1/14—Details; Accessories therefor
    • A61J1/1475—Inlet or outlet ports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/325—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polycycloolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/246—All polymers belonging to those covered by groups B32B27/32 and B32B27/30
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/31—Heat sealable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/582—Tearability
    • B32B2307/5825—Tear resistant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/702—Amorphous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/46—Bags
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/80—Medical packaging

Landscapes

  • Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Hematology (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Medical Preparation Storing Or Oral Administration Devices (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)

Abstract

A laminate comprising a substrate layer comprising a polypropylene resin and a heat-sealing layer comprising a cyclic polyolefin which is a hydrogenated block copolymer having hydrogenated aromatic vinyl polymer block units which are hydrogenated products of polymer blocks composed of aromatic vinyl monomer units and hydrogenated conjugated diene polymer block units which are hydrogenated products of polymer blocks composed of conjugated diene monomer units, wherein the hydrogenated block copolymer has at least 2 of the hydrogenated aromatic vinyl polymer block units and at least 1 of the hydrogenated conjugated diene polymer block units.

Description

Laminate, container, and infusion bag
Technical Field
The present invention relates to a laminate having gas barrier properties and having the properties of a synthetic resin that can be sterilized at high temperatures, and having excellent transparency, impact resistance, mechanical strength, and heat sealability, and a container such as a medical container and an infusion bag using the laminate.
Background
The cyclic polyolefin has a lower mechanical strength than a polymer composed of a chain hydrocarbon such as polyethylene or polypropylene, and also has a poor affinity (adhesiveness) with other resins. However, cyclic polyolefins are excellent in transparency, low in reactivity (adsorbability) with contents, stable against reagents such as acids and alkalis, and have various characteristics required for containers such as medical containers.
In view of this, many proposals have been made to improve mechanical properties by laminating another resin layer as a reinforcing layer on a cyclic polyolefin layer.
As a means for improving the adhesion between the layers when the cyclic polyolefin layer and the other resin layer are laminated, there is a method of roughening the laminated surface by chemical treatment with a reagent, plasma treatment, or the like to increase the surface area.
The following laminates are proposed: a laminate in which a cyclic polyolefin having a ketone group introduced therein by irradiating the laminate surface with ultraviolet light and a resin layer having a group reactive with the ketone group introduced therein are laminated and bonded by bonding of two functional groups (patent document 1).
A polypropylene resin has excellent properties as a material for containers such as heat resistance compared with a polyethylene resin, but because of its weak adhesion to a cyclic polyolefin, a film in which a resin layer obtained by adding polypropylene or the like to a linear low-density polyethylene produced using a single-site catalyst is laminated as an intermediate layer (adhesive layer) between two layers has been proposed (patent document 2).
A medical container in which a cyclic polyolefin layer and a high-density polyethylene layer are laminated without an adhesive layer interposed therebetween has been proposed (patent document 3).
A multilayer container in which a cyclic polyolefin and a polypropylene resin are laminated without using an adhesive has been proposed (patent document 4). In this multilayer container, a large amount of styrene elastomer needs to be added to the polypropylene resin layer, which causes a problem that the heat resistance of the polypropylene resin layer is impaired.
Patent document 1: japanese patent laid-open No. 2003-25506
Patent document 2: japanese patent laid-open No. 2005-335108
Patent document 3: japanese patent laid-open No. 2008-18063
Patent document 4: japanese patent laid-open publication No. 2011-93209
Various developments have been made in the past for the lamination of: in a container or a medical container provided with a cyclic polyolefin layer, while the properties inherent in cyclic polyolefin as a container material are maintained, the mechanical strength (improvement in brittleness), heat sealability, and the like are improved. However, although the mechanical properties of the cyclic polyolefin can be improved by laminating other resin layers such as polyethylene or polypropylene, the transparency of the cyclic polyolefin is reduced by laminating these other resin layers.
In particular, when the laminate is used for a medical container, a high-temperature sterilization treatment is required before use, and therefore, from the viewpoint of heat resistance, a polypropylene resin is often used as a base material.
Therefore, if an adhesive layer is provided between the polypropylene resin and the cyclic polyolefin layer as in the conventional case, there is a possibility that the components in the adhesive layer may be mixed into the drug (medicament) in the container. Therefore, a container or a medical container made of a laminate without using an adhesive layer has been desired.
Disclosure of Invention
The purpose of the present invention is to provide a laminate which is a laminate comprising a base layer made of a polypropylene resin and a heat-sealing layer made of a cyclic polyolefin, has less influence on transparency due to the cyclic polyolefin, can be laminated without using an adhesive layer, and has excellent heat sealability while maintaining heat resistance, and a container or an infusion bag such as a medical container comprising the laminate.
The present inventors have conducted extensive studies on a cyclic polyolefin having an adhesive force necessary for lamination of a polypropylene resin layer and excellent heat sealability, and as a result, have found that: among the cyclic polyolefins, a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least 2 polymer blocks P derived from an aromatic vinyl monomer and at least 1 polymer block Q derived from a conjugated diene monomer has higher transparency and higher heat seal strength at high temperatures when it is laminated with a polypropylene resin layer than in the case of a cyclic polyolefin or the like formed from a conventional monomer having a norbornene skeleton.
It was also found that: the specific hydrogenated block copolymer is excellent in adhesion to a polyolefin resin, can be easily formed into a laminate or a container by coextrusion molding or the like without using an adhesive layer which has been conventionally required for adhesion between a polypropylene resin layer and a cyclic polyolefin layer, and is most suitable as a medical container having storability and visibility of contents from the viewpoint of excellent transparency, heat resistance and heat sealability, thereby completing the present invention.
Namely, the present invention has the following features.
[1] A laminate comprising a substrate layer comprising a polypropylene resin and a heat-sealing layer comprising a cyclic polyolefin which is a hydrogenated block copolymer having hydrogenated aromatic vinyl polymer block units which are hydrogenated products of polymer blocks composed of aromatic vinyl monomer units and hydrogenated conjugated diene polymer block units which are hydrogenated products of polymer blocks composed of conjugated diene monomer units, wherein the hydrogenated block copolymer has at least 2 of the hydrogenated aromatic vinyl polymer block units and at least 1 of the hydrogenated conjugated diene polymer block units.
[2] The laminate according to [1], wherein the adhesive strength (before heat treatment) between the base layer comprising the polypropylene resin and the heat seal layer comprising the cyclic polyolefin is 30N/15mm or more.
[3] The laminate according to [1] or [2], wherein the adhesive strength (after heat treatment) between the base layer comprising the polypropylene-based resin and the heat-seal layer comprising the cyclic polyolefin is 30N/15mm or more.
[4] A container comprising a laminate having a substrate layer comprising a polypropylene resin and a heat-seal layer comprising a cyclic polyolefin, wherein the heat-seal layer of the laminate is bonded to each other, and the cyclic polyolefin is a hydrogenated block copolymer having a hydrogenated aromatic vinyl polymer block unit which is a hydrogenated product of a polymer block comprising an aromatic vinyl monomer unit and a hydrogenated conjugated diene polymer block unit which is a hydrogenated product of a polymer block comprising a conjugated diene monomer unit, the hydrogenated block copolymer having at least 2 of the hydrogenated aromatic vinyl polymer block units and at least 1 of the hydrogenated conjugated diene polymer block units.
[5] The container according to [4], wherein the hydrogenated aromatic vinyl polymer block unit has a degree of hydrogenation of 90% or more, and the hydrogenated conjugated diene polymer block unit has a degree of hydrogenation of 95% or more.
[6] The container according to [4] or [5], wherein the hydrogenated aromatic vinyl polymer block unit is composed of hydrogenated polystyrene, and the content of the hydrogenated polystyrene in the cyclic polyolefin is 50 to 99 mol%.
[7] The container according to any one of [4] to [6], wherein the hydrogenated conjugated diene polymer block unit is composed of hydrogenated polybutadiene, and the content of the hydrogenated polybutadiene in the cyclic polyolefin is 1 to 50 mol%.
[8] The container according to any one of [4] to [7], which is formed by directly laminating the base material layer and the heat seal layer.
[9] The container according to any one of [4] to [8], which is obtained by directly laminating the polypropylene resin of the base layer and the heat seal layer.
[10] The container according to any one of [4] to [9], wherein the base layer is made of a polypropylene resin.
[11] A medical container comprising the container according to any one of [4] to [10 ].
[12] An infusion bag comprising the medical container as set forth in [11 ].
[13] The infusion bag according to [12], which has a mouthpiece.
[14] The infusion bag according to [13], wherein the interface portion comprises a polypropylene resin.
[15] The infusion bag according to [13] or [14], which is formed by directly heat-sealing the interface part and the heat seal layer.
[16] The infusion bag according to any one of [13] to [15], wherein the interface is made of a polypropylene resin.
[17] A medical container comprising a laminate comprising a base layer and a heat-seal layer, wherein the base layer comprises a polypropylene resin, the heat-seal layer comprises a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least 2 polymer blocks P derived from a vinyl aromatic compound and at least 1 polymer block Q derived from a conjugated diene, and the heat-seal layer of the laminate is joined to each other.
Effects of the invention
In the present invention, the specific hydrogenated block copolymer used for the heat seal layer is excellent in heat sealability and high in adhesion to the polypropylene resin, and can be easily molded into a laminate or a container by coextrusion molding or the like without interposing an adhesive layer therebetween, and excellent adhesion to the polypropylene resin can be obtained. Further, since the container is excellent in transparency and adhesive strength even at high temperatures and an adhesive layer is not used, there is no fear that impurities are mixed into contents (drugs, chemical solutions) and the like, and the container is excellent in the storage property of contents and visibility as a medical container.
Detailed Description
The present invention will be described in detail below, but the following description is an example of an embodiment of the present invention, and the present invention is not limited to the contents described below as long as the present invention does not exceed the gist of the present invention, and can be arbitrarily modified and implemented within a range not departing from the gist of the present invention.
Hereinafter, "to" is used as a range including values before and after the "to" when the "to" is used before and after the "to" indicates that the "to" includes a numerical value or a physical property value.
The laminate of the present invention is a laminate having a base layer comprising a polypropylene-based resin and a heat seal layer comprising a cyclic polyolefin, wherein the cyclic polyolefin is a hydrogenated block copolymer having hydrogenated aromatic vinyl polymer block units which are hydrogenated products of polymer blocks composed of aromatic vinyl monomer units and hydrogenated conjugated diene polymer block units which are hydrogenated products of polymer blocks composed of conjugated diene monomer units, and the hydrogenated block copolymer has at least 2 of the hydrogenated aromatic vinyl polymer block units and at least 1 of the hydrogenated conjugated diene polymer block units.
The container of the present invention is a container comprising a laminate having a base layer comprising a polypropylene-based resin and a heat-seal layer comprising a cyclic polyolefin, and the heat-seal layer of the laminate is joined to each other, wherein the cyclic polyolefin is a hydrogenated block copolymer having a hydrogenated aromatic vinyl polymer block unit which is a hydrogenated product of a polymer block comprising an aromatic vinyl monomer unit and a hydrogenated conjugated diene polymer block unit which is a hydrogenated product of a polymer block comprising a conjugated diene monomer unit, and the hydrogenated block copolymer has at least 2 of the hydrogenated aromatic vinyl polymer block units and at least 1 of the hydrogenated conjugated diene polymer block units.
That is, the container or medical container of the present invention is a container or medical container comprising a laminate comprising a base layer and a heat seal layer, wherein the base layer comprises a polypropylene-based resin, and the heat seal layer of the laminate is joined to each other, and is characterized in that the heat seal layer comprises a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least 2 polymer blocks P derived from a vinyl aromatic compound and at least 1 polymer block Q derived from a conjugated diene.
In the present specification, the "hydrogenated block copolymer" is sometimes also referred to as "hydrogenated block copolymer".
In addition, in the present specification, "a hydrogenated block copolymer" (water added ブロック co-polymer) or "a hydrogenated block copolymer" (water hydrogenated ブロック コ ポ リ マ ー) "may be expressed as" a hydrogenated block copolymer having hydrogenated aromatic vinyl polymer block units, which are hydrogenated products of a polymer block composed of aromatic vinyl monomer units, and hydrogenated conjugated diene polymer block units, which are hydrogenated products of a polymer block composed of conjugated diene monomer units, and having at least 2 hydrogenated aromatic vinyl polymer block units and at least 1 hydrogenated conjugated diene polymer block unit ".
The cyclic polyolefin of the present invention is a resin composed of the above hydrogenated block copolymer. That is, the cyclic polyolefin according to the present invention is a resin composed of the hydrogenated block copolymer.
The "cyclic" of the "cyclic polyolefin" refers to an alicyclic structure resulting from hydrogenation of an aromatic ring included in the hydrogenated aromatic vinyl polymer block unit.
Hereinafter, the laminate constituting the container or medical container of the present invention may be referred to as "the laminate of the present invention", and the base material layer and the heat-seal layer in the laminate may be referred to as "the base material layer of the present invention" and "the heat-seal layer of the present invention", respectively. The polypropylene-based resin in the base layer is referred to as "the polypropylene-based resin of the present invention", and the specific hydrogenated block copolymer in the heat seal layer is referred to as "the hydrogenated block copolymer of the present invention", or "the cyclic polyolefin of the present invention".
< mechanism >
In the container or medical container of the present invention, the hydrogenated block copolymer of the present invention used for the heat seal layer is a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least 2 polymer blocks P derived from an aromatic vinyl monomer (hereinafter, sometimes simply referred to as "blocks P") and at least 1 polymer block Q derived from a conjugated diene monomer (hereinafter, sometimes simply referred to as "blocks Q"). Since the hydrogenated product of the block copolymer having at least 2 blocks P and at least 1 block Q in this manner exhibits excellent adhesion to the polypropylene-based resin of the substrate layer and heat sealability.
Further, since the hydrogenated block copolymer is amorphous and has a high heat distortion temperature, it is excellent in heat resistance and also excellent in transparency and transparency after heat treatment.
< Heat sealing layer >
In the present invention, "heat seal" is a term indicating "hot-melt adhesiveness to an adherend". The term "heat-sealable layer" is used to mean a layer having a hot-melt adhesive property to an adherend. These terms are commonly used by those skilled in the art.
The heat-seal layer of the present invention comprises the hydrogenated block copolymer of the present invention, i.e., the cyclic polyolefin of the present invention. The heat-sealable layer of the present invention may contain only 1 kind of the hydrogenated block copolymer of the present invention, or may contain 2 or more kinds of hydrogenated block copolymers having different compositions, physical properties, and the like.
The heat-seal layer of the present invention is a layer containing the hydrogenated block copolymer of the present invention, but may contain a polyethylene resin, a polypropylene resin, a styrene elastomer, and the like within a range not impairing the physical properties, particularly transparency, of the medical container. However, in addition to the effects obtained by using the hydrogenated block copolymer of the present invention, the proportion of the hydrogenated block copolymer of the present invention contained in the heat seal layer is usually 35% by weight or more, preferably 40 to 100% by weight.
< hydrogenated Block copolymer >
The hydrogenated block copolymer of the present invention is a hydrogenated block copolymer obtained by hydrogenating (hereinafter, sometimes referred to as "hydrogenation") a block copolymer having at least 2 polymer blocks P derived from an aromatic vinyl monomer and at least 1 polymer block Q derived from a conjugated diene monomer (hereinafter, sometimes referred to as "block copolymer of the present invention").
Hereinafter, a block hydrogenated for the block P is referred to as a "hydrogenated block P", and a block hydrogenated for the block Q is referred to as a "hydrogenated block Q".
The hydrogenated block copolymer of the present invention can also be represented as follows.
The hydrogenated block copolymer of the present invention has hydrogenated aromatic vinyl polymer block units that are hydrides of polymer blocks composed of aromatic vinyl monomer units and hydrogenated conjugated diene polymer block units that are hydrides of polymer blocks composed of conjugated diene monomer units, and has at least 2 hydrogenated aromatic vinyl polymer block units and at least 1 hydrogenated conjugated diene polymer block unit.
The aromatic vinyl monomer as a raw material of the hydrogenated block copolymer is a monomer represented by the following formula (1).
[ chemical formula 1]
Figure BDA0002675745010000081
Where R is hydrogen or alkyl, Ar is phenyl, halophenyl, alkylphenyl, alkylhalophenyl, naphthyl, pyridinyl or anthracenyl.
The alkyl group includes 1 to 6 carbon atoms, and the 1 to 6 carbon atoms may be mono-or poly-substituted with such functional groups as a halogen group, a nitro group, an amino group, a hydroxyl group, a cyano group, a carbonyl group and a carboxyl group.
Ar is preferably phenyl or alkylphenyl, more preferably phenyl.
Examples of the aromatic vinyl monomer include all isomers of styrene, α -methylstyrene, vinyltoluene, ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures of these monomers. Styrene and alpha-methylstyrene are preferred, and styrene is more preferred.
The conjugated diene monomer as a raw material of the hydrogenated block copolymer may be any monomer having 2 conjugated double bonds, and examples thereof include 1, 3-butadiene, 2-methyl-1, 3-butadiene (isoprene), 2-methyl-1, 3-pentadiene, analogous compounds thereof, and mixtures thereof. Preferably 1, 3-butadiene, isoprene, more preferably 1, 3-butadiene.
The block P is preferably a polystyrene block.
The block Q is preferably a polybutadiene block.
The polybutadiene that is a polymer of 1, 3-butadiene may include any of 1,2 configuration that brings an equivalent of a 1-butene repeating unit by hydrogenation or 1,4 configuration that brings an equivalent of an ethylene repeating unit by hydrogenation.
The block copolymer and the hydrogenated block copolymer of the present invention are preferably a block copolymer and a hydrogenated block copolymer having no functional group. Here, "no functional group" means that no group containing atoms other than carbon atoms and hydrogen atoms is present in the block copolymer and the hydrogenated block copolymer.
As a preferred example of the hydrogenated block P, that is, the hydrogenated aromatic vinyl polymer block unit, hydrogenated polystyrene can be mentioned.
Preferred examples of the hydrogenated block Q, i.e., the hydrogenated conjugated diene polymer block unit, include hydrogenated polybutadiene.
A preferred embodiment of the hydrogenated block copolymer includes a hydrogenated triblock or pentablock copolymer of styrene and butadiene. The hydrogenated block copolymer is preferably free of any other functional groups or structural modifiers.
By "block" is defined to mean a polymeric segment of a copolymer that is separated from microlayers of structurally or compositionally different polymeric segments of the copolymer. Microlayer separation results from the fact that the polymeric segments in the block copolymer do not intermix.
Microlayer separation and block copolymers are widely discussed in PHYSSICS TODAY, BlockCopolymers-Designer Soft Materials, 1999, 2.months 32-38.
The content of the hydrogenated block P in the hydrogenated block copolymer is preferably 50 to 99 mol%, more preferably 60 to 90 mol%.
If the content of the hydrogenated block P is not less than the lower limit, the rigidity is not lowered, and if the content is not more than the upper limit, the brittleness is not deteriorated.
The content of the hydrogenated block Q in the hydrogenated block copolymer is preferably 1 to 50 mol%, more preferably 10 to 40 mol%.
If the content of the hydrogenated block Q is not less than the lower limit, brittleness will not be deteriorated, and if it is not more than the upper limit, rigidity will not be decreased.
Hydrogenated block copolymers are made from the hydrogenation of block copolymers including triblock, multiblock, tapered and radial block copolymers such as SBS, SBSBS, SIS, SISIS and SISBS (where S refers to polystyrene, B refers to polybutadiene, and I refers to polyisoprene).
The hydrogenated block copolymer contains a segment composed of an aromatic vinyl polymer at each end. Thus, the hydrogenated block copolymer of the present invention has at least 2 hydrogenated aromatic vinyl polymer block units (hydrogenated block P). Between the 2 hydrogenated aromatic vinyl polymer block units, there are at least 1 hydrogenated conjugated diene polymer block unit (hydrogenated block Q).
The block copolymer before hydrogenation constituting the hydrogenated block copolymer may contain several additional blocks, and these blocks may be incorporated at arbitrary positions of the triblock polymer backbone. Thus, the linear blocks include, for example, SBS, SBSB, SBSBs, and sbsbsbsb. The copolymer may be branched and the polymeric chains may be attached at any position along the backbone of the copolymer.
The hydrogenated block copolymer of the present invention preferably has a high hydrogenation ratio of the respective blocks P, Q from the viewpoint of adhesion to the polypropylene resin of the substrate layer. The "hydrogenation rate" can also be expressed as "hydrogenation degree".
Preferably, the hydrogenation rate of the hydrogenated block P is 90% or more, and the hydrogenation rate of the hydrogenated block Q is 95% or more. More preferably, the hydrogenation rate of the hydrogenated block P is 95% or more, and the hydrogenation rate of the hydrogenated block Q is 99% or more. It is more preferable that the hydrogenation rate of the hydrogenated block P is 98% or more and the hydrogenation rate of the hydrogenated block Q is 99.5% or more, and it is most preferable that the hydrogenation rate of the hydrogenated block P is 99.5% or more and the hydrogenation rate of the hydrogenated block Q is 99.5% or more.
Here, the "hydrogenation ratio" refers to a ratio at which unsaturated bonds before hydrogenation are hydrogenated and saturated. The hydrogenation rate of the hydrogenated block P, Q was determined by proton NMR.
The lower limit of the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 30,000 or more, more preferably 40,000 or more, still more preferably 45,000 or more, and most preferably 50,000 or more. The upper limit of the weight average molecular weight (Mw) of the hydrogenated block copolymer is preferably 120,000 or less, more preferably 100,000 or less, still more preferably 95,000 or less, most preferably 90,000 or less, particularly preferably 85,000 or less, and very preferably 80,000 or less.
The weight average molecular weight (Mw) of the hydrogenated block copolymer of the present invention is a value in terms of polystyrene determined by Gel Permeation Chromatography (GPC).
The hydrogenated block copolymer preferably has the following physical properties.
Density (ASTM D792): 0.92 to 0.96g/cm3
MFR (ISO R1133 (measured temperature 230 ℃ C., load 2.16 kg): 1-300 g/10 min
Glass transition temperature (Tg): 110-135 deg.C
Flexural modulus of elasticity (ISO 178): 1500-2700 MPa
When the density is not less than the lower limit, the heat resistance is good, and when the density is not more than the upper limit, the impact resistance and the flexibility are good.
If MFR (melt flow rate) is within the above range, it is preferable from the viewpoint of moldability.
If the flexural modulus is not less than the lower limit, the heat sealability is good, and if the flexural modulus is not more than the upper limit, the impact resistance and flexibility are good.
From the viewpoint of heat resistance and sterilization treatment, the Tg is preferably 110 ℃ or higher, more preferably 115 ℃ or higher.
As the cyclic polyolefin which is the hydrogenated block copolymer of the present invention, commercially available ones can be used, and specific examples thereof include those manufactured by Mitsubishi chemical corporation: ZELAS (trade mark registration).
< substrate layer >
The substrate layer of the present invention comprises a polypropylene resin.
The substrate layer may contain only one kind of polypropylene resin, or may contain 2 or more kinds of polypropylene polymers having different compositions, physical properties, and the like.
The base layer contains 70 wt% or more of a polypropylene resin, preferably 80 to 100 wt% of a polypropylene resin.
When the base material layer is composed of a plurality of layers, a layer of polypropylene resin is preferably present on the surface, and this layer is preferably in contact with the heat-seal layer.
The base layer is preferably made of a polypropylene resin.
The base material layer may contain additives used in this field, such as an antioxidant, an antifogging agent, and a lubricant, within a range that does not impair the properties of the medical container, particularly the mechanical strength (impact resistance) and transparency.
Transparent containers are in many cases required in the fields of pharmaceuticals and foods, but there are substances unstable to light in pharmaceuticals, and when such pharmaceuticals are filled, a coloring agent, a light-screening agent such as titanium oxide, or the like may be added.
< Polypropylene resin >
The polypropylene resin of the present invention is a resin containing propylene as a main component. Here, "as a main component" means that the propylene polymer accounts for more than 50% by weight of the resin, and particularly preferably 60% by weight or more of the propylene polymer, and the upper limit of the content thereof is 100% by weight. When the content of the propylene polymer in the polypropylene resin of the present invention is not less than the lower limit, the resulting laminate has good handling properties.
The term "propylene polymer" as used herein means a polymer containing more than 50 mol% of propylene based on the whole monomer components of the starting material.
The polypropylene resin of the present invention may contain components other than the propylene polymer, and may contain, for example, a styrene elastomer and/or a hydrogenated product thereof. The styrene-based elastomer is a polymer having a styrene polymer block and a conjugated diene polymer block, and examples of the conjugated diene polymer block include those derived from butadiene, isoprene, and the like.
When a styrene-based elastomer and/or a hydrogenated product thereof is used, the content thereof is preferably 10 to 40% by weight, more preferably 15 to 30% by weight, based on the total amount of the propylene-based polymer and the styrene-based elastomer and/or the hydrogenated product thereof.
The polypropylene resin of the present invention is preferably a resin having the following physical properties.
Melting point: 121 to 160 DEG C
Density (JIS K7112): 0.88 to 0.91g/cm3
MFR (JIS K7210 (measurement temperature 230 ℃ C., load 2.16 kg): 1.0-10 g/min
Flexural modulus of elasticity (ISO 178): 300 to 1500MPa
When the density of the polypropylene resin of the present invention constituting the base layer is not less than the lower limit, the heat sealability is improved, and when the density is not more than the upper limit, the transparency is improved.
If MFR (melt flow rate) is within the above range, it is preferable from the viewpoint of moldability.
If the flexural modulus is not less than the lower limit, the heat sealability is good, and if the flexural modulus is not more than the upper limit, the impact resistance and flexibility are good.
The melting point is preferably 121 ℃ or higher, more preferably 125 ℃ or higher, from the viewpoint of heat resistance and sterilization treatment. On the other hand, the upper limit of the melting point of the polypropylene resin is usually about 160 ℃.
As the polypropylene resin of the present invention, commercially available resins can be used, and specific examples thereof include Novatec PP, Welnex and Wintec manufactured by Japan Polypropylene Corporation.
< layered product >
The laminate of the present invention has the heat-seal layer of the present invention and the substrate layer of the present invention.
The laminate of the present invention is preferably one in which the heat-seal layer of the present invention and the base material layer of the present invention are directly laminated without interposing an intermediate layer such as an adhesive layer between the heat-seal layer of the present invention and the base material layer of the present invention.
The method for producing the laminate of the present invention may be any method as long as the above layers can be laminated and integrated, and examples thereof include a dry lamination method, an extrusion lamination method, a coextrusion lamination method (T-die method, water-cooling inflation method, air-cooling inflation method), a thermal lamination method, and a lamination method combining these methods.
Among them, the water-cooling inflation method is preferable from the viewpoint of obtaining transparency of the entire laminate and the viewpoint of obtaining internal sealing properties.
In the laminate of the present invention, the thickness of each layer may be appropriately selected depending on the purpose of use. The thickness of the heat-sealing layer is preferably 5 to 100 μm, more preferably 10 to 50 μm. If the thickness of the heat-seal layer is not less than the lower limit, it is preferable from the viewpoint of stability of heat-seal strength, and if it is not more than the upper limit, it is preferable from the viewpoint of flexibility of the entire laminate.
If the heat-seal layer is too thick, the heat-seal layer is highly rigid and easily broken, and if it is too thin, there is a risk that the low adsorption effect of the contents cannot be obtained and the water vapor permeation cannot be suppressed.
In the laminate of the present invention, the thickness of the base material layer is 100 μm or more, for example, preferably 140 to 330 μm, and more preferably 150 to 250 μm. The base material layer is a layer which mainly serves as an outer layer of the laminate and is responsible for improvement of mechanical strength, heat sealability, and the like, but if the thickness of the base material layer is not less than the above lower limit, it is preferable from the viewpoint of mechanical strength, and if it is not more than the above upper limit, it is preferable from the viewpoint of flexibility of the entire laminate.
The thickness ratio of each layer of the laminate of the present invention is preferably (heat seal layer): (substrate layer) ═ 1: 30-1: 3.
the laminate of the present invention preferably has a bonding strength (before heat treatment) of 30N/15mm or more between the base material layer and the heat seal layer, as measured by the method described in the later-described embodiment.
The laminate of the present invention preferably has a bonding strength (after heat treatment) of 30N/15mm or more between the base material layer and the heat seal layer, measured by the method described in the later-described embodiment.
< Container >
As a method for producing a container using the laminate of the present invention, any method such as a sheet molding method (thermoforming method) such as vacuum molding or press molding, a blow molding method such as multilayer coextrusion blow molding, or a method for producing a bag-like object by bonding the peripheral portions of the laminate in the form of blades cut into a predetermined shape by thermal welding (strong welding) or an adhesive can be used.
Examples of applications of the container of the present invention include food applications, industrial material applications, and medical applications.
The shape of the container is not particularly limited, and may be a bottle, a tube, a bag, a cell (cell), or the like.
< medical Container >
As a method for producing a medical container using the laminate of the present invention, any method such as a sheet molding method (thermoforming method) such as vacuum molding or press molding, a blow molding method such as multilayer coextrusion blow molding, or a method for producing a bag by bonding the peripheral portions of the laminate in the form of blades cut into a predetermined shape by thermal welding (strong welding) or an adhesive can be used.
In manufacturing the medical container of the present invention, the weak seal portion that divides the interior of the container into a plurality of storage chambers may be formed by heat-sealing a part of the opposing inner wall surfaces of the container using a seal tape or the like whose heat-sealing temperature is controlled.
The heat-sealing temperature at the time of forming the weak seal part varies depending on the composition of the hydrogenated block copolymer of the present invention, the thickness of the heat-seal layer and the whole laminate, but is usually about 140 to 160 ℃. The heat seal strength of the weak seal portion which can be easily peeled is preferably less than 10N/10mm, more preferably 0.1 to 9N/10mm, as the peel strength measured by the method described in the later-described example.
When the heat seal strength of the weak seal portion is too high, the weak seal portion cannot be easily peeled, and when it is too low, the weak seal portion is peeled by a small impact applied unintentionally, and the object of dividing the storage chamber immediately before use cannot be achieved.
On the other hand, the heat-sealing temperature at which the peripheral portions of the laminated bodies cut into the blade form in a predetermined shape are heat-sealed to form the strong seal portions varies depending on the composition of the hydrogenated block copolymer of the present invention, the thickness of the heat-seal layer and the whole laminated body, but is usually about 180 to 220 ℃. The heat seal strength of the strong seal portion for cutting off the outside (outside air) from the container interior is preferably 10N/10mm or more as the peel strength measured by the method described in the later-described embodiment.
When the heat seal strength of the strong seal portion is too low, the strength required as a multi-chamber container cannot be satisfied. The higher the heat seal strength of the strong seal portion, the better, but the upper limit thereof is usually about 60N/10 mm.
In order to easily control the heat sealing temperature of the weak seal portion and the strong seal portion, the heat sealing temperature at the time of forming the strong seal portion is preferably higher by 10 ℃.
The medical container of the present invention is generally provided as a multi-chamber container having 2 storage chambers by dividing the interior of the container into 2 parts, but is not limited thereto, and may be a container having 3 or more chambers divided by a plurality of linear weak seal portions.
The shape of the medical container of the present invention is not particularly limited, and is a bottle, a tube, a bag, a small chamber, or the like.
< content of medical Container >
The contents such as a drug to be stored in the storage chamber of the medical container of the present invention are not particularly limited. The multi-chamber container of the present invention is suitable for use as a multi-chamber container for containing a high calorie infusion solution or the like comprising amino acids, sugars, electrolytes, vitamins, because of its excellent storage properties and the like.
< infusion bag >
The medical container of the present invention is particularly suitable as an infusion bag.
An infusion bag generally includes a main body of the infusion bag, an inlet port for injecting a drug solution, a cap including a rubber stopper for taking out the drug solution, and the like. In the infusion bag having the mouthpiece, the heat seal layer of the present invention has high weldability to a polypropylene resin generally used in the mouthpiece, and therefore the medical container of the present invention can be easily combined and suitably used.
In the infusion bag of the present invention, the heat-seal layer and the interface unit of the present invention are preferably heat-sealed directly without interposing an intermediate layer such as an adhesive layer between the heat-seal layer and the interface unit of the present invention.
When the interface portion is made of a plurality of materials, it is preferable that a layer of polypropylene resin is formed on the surface and the layer is in contact with the heat seal layer.
The interface is preferably made of polypropylene resin.
The heat seal strength between the interface portion and the heat seal layer of the infusion bag is preferably 10N/10mm or more, more preferably 15N/10mm or more, as the peel strength measured by the method described in the later-described examples.
Although the method of forming an infusion bag using the laminate of the present invention is not limited, a method of forming a tubular (cylindrical) inflation film by coextrusion and welding the ends, or the like, may be preferably employed.
Examples
The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the examples provided below, as long as the gist of the present invention is not exceeded. The values of various manufacturing conditions or evaluation results in the following examples have the meaning of being preferred values of the upper limit or the lower limit in the embodiment of the present invention, and preferred ranges may be ranges specified by a combination of the values of the above upper limit or lower limit and the values of the following examples or values between the examples.
< Melt Flow Rate (MFR) >
An apparatus: "Melt Indexer" manufactured by Toyo Seiki Kabushiki Kaisha "
Temperature: 230 deg.C
The orifice diameter: 2mm
Load: 21.18N
< molecular weight >
An apparatus: "GPC HLC-832 GPC/HT" manufactured by Tosoh corporation "
The detector: "1A Infrared Spectrophotometer" (measurement wavelength 3.42 μm) manufactured by MIRAN corporation
Column chromatography: showa Denko K.K. "AD 806M/S" 3
Calibration of the column: monodisperse polystyrene (each 0.5mg/ml solution of A500, A2500, F1, F2, F4, F10, F20, F40, and F288) manufactured by Tosoh was measured, and the logarithm of the elution volume and the molecular weight was approximated by a cubic equation.
Measurement temperature: 135 deg.C
Concentration: 20mg/10mL
Injection amount: 0.2ml
Solvent: ortho-dichlorobenzene
Flow rate: 1.0 ml/min
< ratio of Polymer blocks >
[ measurement by carbon NMR ]
An apparatus: the "AVANCE 400 spectrometer" manufactured by Bruker "
Solvent: o-dichlorobenzene-h 4/p-dichlorobenzene-d 4 mixed solvent
Concentration: 0.3g/2.5mL
Measurement of:13C-NMR
resonance frequency: 400MHz
Cumulative number of times: 1536
The pour angle: 45 degree
Data acquisition time: 1.5 seconds
Pulse repetition time: 15 seconds
Measurement temperature: 100 deg.C
·1H, irradiation: complete decoupling
< hydrogenation ratio of hydrogenated Block P (hydrogenated aromatic vinyl Polymer Block Unit) and hydrogenation ratio of hydrogenated Block Q (hydrogenated Co-diene Polymer Block Unit) >
[ measurement by proton NMR ]
An apparatus: "400 YH spectrometer" manufactured by Nippon spectral Co., Ltd "
Solvent: deuterated chloroform
Concentration: 0.045g/1.0mL
Measurement of:1H-NMR
resonance frequency: 400MHz
Cumulative number of times: 8
Measurement temperature: 18.5 deg.C
Hydrogenation rate of hydrogenated block P: integral value reduction rate of 6.8 to 7.5ppm
Hydrogenation rate of hydrogenated block Q: integral value reduction rate of 5.7 to 6.4ppm
[ raw materials ]
The raw materials used in the following examples and comparative examples are as follows.
< ingredient a: resin for Heat-sealable layer >
[ A-1 Cyclic polyolefin ]
The hydrogenated block copolymer "ZELAS (registered trademark)" of the present invention was manufactured by Mitsubishi chemical corporation "
Density (ASTM D792): 0.94g/cm3
MFR (230 ℃, 2.16kg (ISO R1133)): 20.0g/10 min
·Tg：117℃
Flexural modulus of elasticity (ISO 178): 2,500MPa
·Mw：54,200
Hydrogenated block P: hydrogenated polystyrene having a content of 60 mol% and a hydrogenation rate of 99.5% or more
Hydrogenated block Q: hydrogenated polybutadiene having a content of 40 mol% and a hydrogenation rate of 99.5% or more
Block structure: pentablock structure, total hydrogenation rate more than 99.5%
[ A-2 Cyclic polyolefin ]
The hydrogenated block copolymer "ZELAS (registered trademark) mc 930" of the present invention manufactured by Mitsubishi chemical corporation "
Density (ASTM D792): 0.94g/cm3
MFR (230 ℃, 2.16kg (ISO R1133)): 1.3g/10 min
·Tg：129℃
Flexural modulus of elasticity (ISO 178): 2,600MPa
·Mw：75,600
Hydrogenated block P: hydrogenated polystyrene having a content of 65 mol% and a hydrogenation rate of 99.5% or more
Hydrogenated block Q: hydrogenated polybutadiene having a content of 35 mol% and a hydrogenation rate of 99.5% or more
Block structure: pentablock structure, total hydrogenation rate more than 99.5%
[ a-1 Cyclic polyolefin ]
A cyclic polyolefin polymer (a ring-opened polymer of a norbornene-based monomer) "ZEONOR (registered trademark) 1020R", manufactured by Nippon Raceku K.K.) "
Density (ASTM D792: 1.01 g/cm)3
MFR (230 ℃, 2.16kg (ISO R1133): 3g/10 min
·Tg：102℃
Flexural modulus of elasticity (ISO 178): 2,100MPa
[ a-2 Cyclic polyolefin ]
Cyclic polyolefin copolymer (norbornene-ethylene copolymer) "TOPAS (registered trademark) 8007F-04", manufactured by Baoli plastics Co., Ltd "
Density (ISO 1183): 1.01g/cm3
MFR (230 ℃, 2.16kg (ISO R1133)): 12.6g/10 min
·Tg：78℃
Flexural modulus of elasticity (ISO 178): 2,500MPa
< component B: resin for base layer >
[ B-1: polypropylene resin
"Novatec PP FW 4B" manufactured by Japan Polypropylene Corporation "
Content of propylene unit: 96% by weight
Melting point: 140 deg.C
Density (JIS K7112): 0.90g/cm3
MFR (230 ℃, 2.16kg (JIS K7210)): 7g/10 min
Flexural modulus of elasticity (ISO 178): 850MPa
[ B-2: polypropylene resin
"Novatec PP FL 4" manufactured by Japan Polypropylene Corporation "
Content of propylene unit: 100% by weight
Melting point: 160 deg.C
Density (JIS K7112): 0.90g/cm3
MFR (230 ℃, 2.16kg (JIS K7210)): 5g/10 min
Flexural modulus of elasticity (ISO 178): 1,400MPa
Examples 1 to 4 comparative examples 1 to 3
< preparation of film for evaluation >
A2-layer film for evaluation was produced by co-extruding the cyclic polyolefin and the polypropylene resin shown in Table 1 at a molding temperature of 250 ℃ using a 2-layer sheet molding machine, to have a thickness of 200 μm (cyclic polyolefin layer: 100 μm/polypropylene resin: 100 μm).
In comparative example 3, since a large number of craters (fish eye) occurred in the film obtained in the production of the film for evaluation, the following evaluation was not performed.
In addition, all the films for evaluation were produced for evaluation, and were not films having a practically optimal thickness range.
< production of evaluation Container >
The obtained film for evaluation was cut into 80X 100mm, 2 sheets thereof were taken out, and the cyclic polyolefin layers were stacked in opposition to each other and heat-sealed using a heat sealer (manufactured by Kagaku Co., Ltd.) under the following conditions, to thereby prepare a container having an overall size of 80X 100 mm. The inside of the container was filled with about 50cc of water as a container for evaluation.
Pressure: 0.3MPa
Time: 3.0 second
Sealing strips: 10mm
Temperature: 240 ℃ C
< high temperature and high pressure Sterilization treatment >
The obtained film for evaluation and the evaluation container were put in a high-temperature high-pressure conditioning and sterilizing tester ("RCS-40 RTGN type" manufactured by saka corporation), and then the atmosphere temperature was increased to 121 ℃ under pressure, and the temperature was maintained for 30 minutes. Thereafter, the test piece was cooled to about 40 ℃ and the film for evaluation and the evaluation container were taken out of the test machine. Hereinafter, the evaluation film and the evaluation container subjected to the sterilization treatment are referred to as an evaluation film after the heat treatment and an evaluation container after the heat treatment, respectively, and the evaluation film before the sterilization treatment is referred to as an evaluation film before the heat treatment.
< measurement of HAZE (HAZE) >
The HAZE of the film was measured for the film before heat treatment and the film after heat treatment according to JIS K7136, and the transparency of the film was evaluated. The results are shown in Table 1.
< evaluation of adhesive Strength >
The film for evaluation before the heat treatment and the film for evaluation after the heat treatment were cut into a strip shape having a width of 15mm, and a T-peel test was performed between the base material layer and the heat seal layer at a speed of 100 mm/min at 23 ℃ according to JIS K6854. The results are shown in Table 1.
When the adhesive strength became 30N/15mm or more, the value of the adhesive strength could not be measured. This case is denoted as "cannot be peeled".
< evaluation of ability to maintain sealed portion >
Whether or not the sealed portion of the evaluation container after the heat treatment was maintained was evaluated by the following criteria. The results are shown in Table 1.
O: there was no water leakage in the state of being taken out from the testing machine, and there was no water leakage even if the container was squeezed.
X: water leakage occurred when the test piece was removed from the test machine.
< evaluation of Heat seal Strength >
The films for evaluation before the heat treatment of examples 1 and 3 and comparative example 1 were cut into pieces of 100mm × 100mm, 2 pieces of the pieces were taken, the cyclic polyolefin layers were stacked in opposition to each other, and heat-sealed using a heat sealer (manufactured by Limited Kagaku corporation) under the following conditions, and the center portion in the longitudinal direction of the films for evaluation was heat-sealed to a width of 10 mm.
Pressure: 0.3MPa
Time: 3.0 second
Sealing strips: 10mm
Temperature: 140-220 deg.C
After that, the peel strength was measured by pulling and peeling the portions of the film for evaluation that were not heat-sealed in opposite directions from each other. The results are shown in Table 1. As described above, the heat seal strength is less than 10N/10mm, preferably 0.1 to 9N/10mm, in the weak seal portion. The strong seal portion is preferably 10N/10mm or more, and therefore 10N/10mm is preferable.
[ Table 1]
Figure BDA0002675745010000221
[ evaluation results ]
As shown in table 1, it can be seen that: in examples 1 to 4 in which the hydrogenated block copolymer of the present invention was used for the heat seal layer, the adhesion to the base material layer was very good, and the haze after the heat treatment was not significantly increased as compared to that before the heat treatment. The heat sealability was also very good, and no water leakage occurred from the evaluation container after the heat treatment.
In comparative examples 1 and 2 in which a cyclic polyolefin that is a ring-opened polymer of a norbornene-based monomer was used for the heat seal layer, the adhesiveness to the base material layer was poor and the increase in haze due to the heat treatment was large. Further, since the heat sealability was not good, water leakage occurred from the evaluation container after the heat treatment. Therefore, it is found that the present invention is not suitable for medical containers requiring heat resistance and sterilization treatment.
In comparative example 3 in which a cyclic polyolefin, which is a copolymer of a monomer having a norbornene skeleton and ethylene, was used as a heat seal layer, many shrinkage cavities were generated at the time of film formation, and a practical laminate could not be obtained.
< evaluation of Heat seal Strength to interface portion >
The films for evaluation of examples 1 to 4 and comparative example 1 before heat treatment and a homopolypropylene sheet having a thickness of 2mm prepared by injection molding ("Novatec PP MA 3" from Japan Polypropylene Corporation) were used, and the cyclic polyolefin layer and the homopolypropylene sheet were superimposed on each other in an opposed manner, and heat-sealed by a heat-sealing machine (manufactured by zukawa Corporation) under the following conditions to heat-seal the central portion in the longitudinal direction of the films for evaluation to a width of 10 mm.
Here, a homopolypropylene sheet having a thickness of 2mm is an article imitating the interface portion of an infusion bag. The evaluation results herein refer to the heat seal strength between the interface part and the heat seal layer in the infusion bag.
Pressure: 0.2MPa
Time: 2.0 second
Sealing strips: width of 10mm
Temperature: 200-240 deg.C
Thereafter, the portion of the film for evaluation which was not heat-sealed was pulled in the opposite direction from the homopolypropylene sheet (in the table, "homopolypropylene sheet") and peeled, thereby measuring the peel strength. The results are shown in Table 2.
The heat seal strength corresponds to the weld strength with the interface portion of the medical container, and is preferably 10N/10mm or more, more preferably 15N/10mm or more.
In Table 2, the area indicated by "-" was not measured.
[ Table 2]
Figure BDA0002675745010000241
[ evaluation results ]
As shown in Table 2, it is understood that the heat-sealing properties with respect to the homopolypropylene sheet are very good in examples 1 to 4 in which the hydrogenated block copolymer of the present invention is used in the heat-seal layer.
On the other hand, it is found that comparative example 1, in which a cyclic polyolefin resin which is a ring-opened polymer of a norbornene-based monomer is used for the heat seal layer, is not suitable for the heat seal layer of the infusion bag having an interface portion of homopolypropylene because of poor heat sealability with the homopolypropylene sheet.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes can be made therein without departing from the spirit and scope thereof.
The present application is based on japanese patent application 2018-089971 filed on 8.5.2018, which is incorporated by reference in its entirety.

Claims (17)

1. A laminate comprising a substrate layer comprising a polypropylene resin and a heat-sealing layer comprising a cyclic polyolefin,
the cyclic polyolefin is a hydrogenated block copolymer having hydrogenated aromatic vinyl polymer block units which are hydrogenated products of polymer blocks composed of aromatic vinyl monomer units and hydrogenated conjugated diene polymer block units which are hydrogenated products of polymer blocks composed of conjugated diene monomer units,
the hydrogenated block copolymer has at least 2 block units of the hydrogenated aromatic vinyl polymer and at least 1 block unit of the hydrogenated conjugated diene polymer.
2. The laminate according to claim 1, wherein the adhesion strength between the base layer comprising the polypropylene-based resin and the heat seal layer comprising the cyclic polyolefin is 30N/15mm or more before the heat treatment.
3. The laminate according to claim 1 or 2, wherein the adhesion strength between the base layer comprising the polypropylene-based resin and the heat seal layer comprising the cyclic polyolefin is 30N/15mm or more after the heat treatment.
4. A container comprising a laminate having a base layer comprising a polypropylene resin and a heat-seal layer comprising a cyclic polyolefin, wherein the heat-seal layers of the laminate are bonded to each other,
the cyclic polyolefin is a hydrogenated block copolymer having hydrogenated aromatic vinyl polymer block units which are hydrogenated products of polymer blocks composed of aromatic vinyl monomer units and hydrogenated conjugated diene polymer block units which are hydrogenated products of polymer blocks composed of conjugated diene monomer units,
the hydrogenated block copolymer has at least 2 block units of the hydrogenated aromatic vinyl polymer and at least 1 block unit of the hydrogenated conjugated diene polymer.
5. The container according to claim 4, wherein the hydrogenated aromatic vinyl polymer block unit has a degree of hydrogenation of 90% or more, and the hydrogenated conjugated diene polymer block unit has a degree of hydrogenation of 95% or more.
6. The container according to claim 4 or 5, wherein the hydrogenated aromatic vinyl polymer block unit is composed of hydrogenated polystyrene, and the content of the hydrogenated polystyrene in the cyclic polyolefin is 50 to 99 mol%.
7. The container according to any one of claims 4 to 6, wherein the hydrogenated conjugated diene polymer block unit is composed of a hydrogenated polybutadiene, and the content of the hydrogenated polybutadiene in the cyclic polyolefin is 1 to 50 mol%.
8. The container according to any one of claims 4 to 7, wherein the base material layer and the heat seal layer are directly laminated.
9. The container according to any one of claims 4 to 8, wherein the heat seal layer is directly laminated with the polypropylene resin of the base material layer.
10. The container according to any one of claims 4 to 9, wherein the base material layer is made of a polypropylene resin.
11. A medical container comprising the container according to any one of claims 4 to 10.
12. An infusion bag comprising the medical container according to claim 11.
13. The infusion bag of claim 12 having an interface portion.
14. The infusion bag according to claim 13, wherein the interface portion comprises a polypropylene-based resin.
15. The infusion bag according to claim 13 or 14, wherein the interface portion and the heat seal layer are directly heat-sealed.
16. The infusion bag according to any one of claims 13 to 15, wherein the interface portion is formed of a polypropylene-based resin.
17. A medical container comprising a laminate comprising a base material layer and a heat seal layer, wherein the base material layer comprises a polypropylene resin and the heat seal layer of the laminate is bonded to each other,
the heat-sealing layer contains a hydrogenated block copolymer obtained by hydrogenating a block copolymer having at least 2 polymer blocks P derived from a vinyl aromatic compound and at least 1 polymer block Q derived from a conjugated diene.
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Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7238578B2 (en) * 2019-04-25 2023-03-14 三菱ケミカル株式会社 Heat-sealable multilayer film and easy-open package
JP7530767B2 (en) 2019-11-12 2024-08-08 Ｍｃｐｐイノベーション合同会社 Thermoplastic resin composition, molded article, and laminate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10180951A (en) * 1996-12-25 1998-07-07 Riken Vinyl Ind Co Ltd Stretch film
WO2007123241A1 (en) * 2006-04-25 2007-11-01 Denki Kagaku Kogyo Kabushiki Kaisha Cover film
JP2009149861A (en) * 2007-11-30 2009-07-09 Sumitomo Chemical Co Ltd Polypropylene resin composition and molded body
EP2311430A1 (en) * 2007-11-22 2011-04-20 Mitsubishi Tanabe Pharma Corporation A plastic container comprising cyclic polyolefin layer
US20140213728A1 (en) * 2011-09-29 2014-07-31 Mitsubishi Chemical Corporation Hydrogenated block copolymer, resin composition, film and container
JP2014208476A (en) * 2013-03-29 2014-11-06 三菱化学株式会社 Laminate
WO2016140322A1 (en) * 2015-03-04 2016-09-09 Ｍｃｐｐイノベーション合同会社 Thermoplastic resin composition, cover member and easily openable container

Family Cites Families (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3333024A (en) * 1963-04-25 1967-07-25 Shell Oil Co Block polymers, compositions containing them and process of their preparation
US5272215A (en) * 1990-08-03 1993-12-21 The West Company, Incorporated Modified plastic elastomer block copolymers
US5352744A (en) * 1993-03-15 1994-10-04 University Of Minnesota Method for hydrogenating polymers and products therefrom
DE19855062A1 (en) * 1998-11-28 2000-05-31 Bayer Ag Block copolymers based on vinylcyclohexane
US6433102B1 (en) * 1998-12-04 2002-08-13 Nippon Zeon Co., Ltd. Hydrogenated polymers, resin composition, and process for producing substrate for information-recording medium
JP4194706B2 (en) * 1999-03-23 2008-12-10 旭化成ケミカルズ株式会社 Cycloolefin resin composition
JP2003502470A (en) * 1999-06-11 2003-01-21 ザ ダウ ケミカル カンパニー Composition comprising hydrogenated block copolymer and its use for end use
US6426390B1 (en) * 1999-06-11 2002-07-30 Dow Global Technology Inc. Hydrogenated block copolymer compositions
EP1310513A4 (en) * 2000-08-04 2006-04-26 Zeon Corp Block copolymer, process for producing the same, and molded object
US6541098B2 (en) * 2000-12-22 2003-04-01 Avery Dennison Corporation Three-dimensional flexible adhesive film structures
JP4421145B2 (en) * 2001-07-02 2010-02-24 Ｓａｂｉｃイノベーティブプラスチックスジャパン合同会社 Piping material
JP2003025506A (en) 2001-07-19 2003-01-29 Asahi Kasei Corp Cyclic polyolefin resin laminate
US20050186377A1 (en) * 2004-02-19 2005-08-25 Hurst William S. Solventless plastic bonding of medical devices and container components through infrared heating
JP2005335108A (en) 2004-05-25 2005-12-08 Toppan Printing Co Ltd Multilayer film and its laminate
US20060089458A1 (en) * 2004-10-22 2006-04-27 Davis John E Articles suitable for autoclave sterilization
EP1840164A1 (en) * 2006-03-30 2007-10-03 SOLVAY INDUSTRIAL FOILS MANAGEMENT AND RESEARCH (Société Anonyme) Retortable composition
US7696270B2 (en) * 2006-06-22 2010-04-13 Eastman Kodak Company Method of manufacturing a wax dispersion
JP5052833B2 (en) 2006-07-13 2012-10-17 株式会社細川洋行 Multilayer body for medical container and medical container
US7576150B2 (en) * 2007-02-28 2009-08-18 Sabic Innovative Plastics Ip B.V. Poly(arylene ether) composition, method, and article
US20100247936A1 (en) * 2009-03-24 2010-09-30 Baxter International Inc. Non-pvc films with tough core layer
EP2436728B1 (en) * 2009-05-28 2018-01-03 The Nippon Synthetic Chemical Industry Co., Ltd. Evoh resin composition, and molded article and multilayer structure both comprising same
AU2010309023B2 (en) * 2009-10-20 2014-03-27 Hosokawa Yoko Co., Ltd. Plastic film and infusion bag
JP5643501B2 (en) 2009-10-30 2014-12-17 キョーラク株式会社 Multi-layer container
US20150290077A1 (en) * 2012-10-25 2015-10-15 Kyoraku Co., Ltd. Medical container
JP6347213B2 (en) * 2012-12-05 2018-06-27 日本ゼオン株式会社 Resin composition and medical drug container using the same
CN108349619B (en) * 2015-10-30 2020-06-30 京洛株式会社 Laminated peeling container
DE102016223980B4 (en) 2016-12-01 2022-09-22 Adidas Ag Process for the production of a plastic molding

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10180951A (en) * 1996-12-25 1998-07-07 Riken Vinyl Ind Co Ltd Stretch film
WO2007123241A1 (en) * 2006-04-25 2007-11-01 Denki Kagaku Kogyo Kabushiki Kaisha Cover film
EP2311430A1 (en) * 2007-11-22 2011-04-20 Mitsubishi Tanabe Pharma Corporation A plastic container comprising cyclic polyolefin layer
JP2009149861A (en) * 2007-11-30 2009-07-09 Sumitomo Chemical Co Ltd Polypropylene resin composition and molded body
US20140213728A1 (en) * 2011-09-29 2014-07-31 Mitsubishi Chemical Corporation Hydrogenated block copolymer, resin composition, film and container
JP2014208476A (en) * 2013-03-29 2014-11-06 三菱化学株式会社 Laminate
WO2016140322A1 (en) * 2015-03-04 2016-09-09 Ｍｃｐｐイノベーション合同会社 Thermoplastic resin composition, cover member and easily openable container

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